CN108603247A - The recovery method of scandium - Google Patents

Abstract

The present invention provides a kind of recovery method of scandium, can efficiently recycle high-grade scandium from nickel oxide ore.The present invention has：Process S1 is leached, the nickel oxide ore containing scandium is leached using sulfuric acid and obtains leachate；Neutralization step S2, in leachate be added neutralizer carry out in and；Vulcanization process S3 adds vulcanizing agent and liquid after being vulcanized after the neutralization in liquid；Ion-exchange process S4, liquid contacts that scandium is made to adsorb with chelating resin after making vulcanization, obtains scandium eluent；Dissolution process S5 adds alkali after obtaining the sediment of scandium hydroxide in scandium eluent, acid solution is added in the scandium hydroxide to obtain the acid dissoluting liquid of scandium；Solvent extraction step S6 makes the acid dissoluting liquid of scandium be contacted with Neutral-neutral Extractants and carries out solvent extraction；It with scandium recovery process S7, adds oxalic acid in raffinate and generates the salt of oxalic acid scandium, roasting obtains scandium oxide.

Description

The recovery method of scandium

Technical field

The present invention relates to a kind of recovery methods of scandium, more specifically, are related to a kind of by the ion based on chelating resin The combination of processing and the solvent extraction processing based on Neutral-neutral Extractants is exchanged come scandium contained in high efficiente callback nickel oxide ore Scandium recovery method.

Background technology

Scandium is exceedingly useful as additive, the electrode material of fuel cell of high-strength alloy.However, because output It is few, it is expensive, so being not up to widely used.

Contain micro scandium in the nickel oxides ore such as laterite, limonite.But nickel oxide ore is because of nickeliferous product Position is relatively low, so not utilized for a long time as nickel raw material industrially.Therefore, also almost without carrying out from nickel oxygen The research of compound ore industrialization recycling scandium.

But in recent years, HPAL techniques are being practical, which is packed into nickel oxide ore together with sulfuric acid adds Pressure vessel heats at a high temperature of 240 DEG C~260 DEG C or so, solid-liquid separation into nickeliferous leachate and leaches residue.At this In HPAL techniques, by adding neutralizer in obtained leachate to make impurity be detached, next, being vulcanized by adding Agent is so as to the recycling nickel in the form of nickel sulfide.Then, by with existing nickel fibers process to obtained nickel sulfide into Row handles to obtain electrical nickel, nickel salt compound.

Using this HPAL techniques, the scandium contained in nickel oxide ore is included in leachate together with nickel In (referring to patent document 1).Moreover, adding neutralizer in the leachate obtained using HPAL techniques to detach impurity and then add After adding vulcanizing agent, nickel is recovered in the form of nickel sulfide.On the other hand, scandium is contained in the acid solution after addition vulcanizing agent In (liquid after vulcanization).Therefore, it is handled using HPAL techniques, nickel and scandium can be efficiently separated.

As the method for recycling scandium from above-mentioned acid solution, it has for instance been proposed that by making scandium be adsorbed in imino group Diacetate detaches for chelating resin of functional group etc. with impurity, by concentrating the method recycled (referring to patent document 2 ~4).

On the other hand, it is also proposed that obtained from the wet type metallurgy using nickel oxide ore by solvent extraction processing To acid solution in recycle scandium method (referring to patent document 5).In method recorded in the patent document 5, first, In addition to scandium also at least containing iron, aluminium, calcium, yttrium, manganese, chromium, magnesium more than one water phase solution containing scandium in, addition kerosene is dilute Organic solvent made of 2- ethylhexyls sulfonic acid-mono- 2- ethylhexyls is released, scandium ingredient is extracted into organic solvent.Thereafter, it is Yttrium, iron, manganese, chromium, magnesium, aluminium, the calcium being extracted out together with scandium in Separation of Organic are added aqueous hydrochloric acid solution and are cleaned After removing them, NaOH aqueous solutions are added in organic solvent, remaining scandium in organic solvent is made to form (OH) containing Sc₃'s Slurry is filtered and obtains Sc (OH)₃Dissolving with hydrochloric acid is used in combination and obtains scandium chloride aqueous solution.Then, in obtained scandium chloride Oxalic acid is added in aqueous solution and forms oxalic acid scandium precipitation, by filtering the precipitation, iron, manganese, chromium, magnesium, aluminium, calcium are separated in filtrate After, the scandium oxide of high-purity is obtained by pre-burning.

But if chelating resin only is used alone, although the distribution into eluent such as iron, aluminium, chromium is very small, Because there are many amount that these impurity include in the feed, in order to be isolated, need to carry out the absorption of plural number time, elution behaviour Make.In addition, absorption, the elution behavior of the multiple several impurities that other deniers include, although strong without scandium, because to washing Distribution in de- liquid is high, so very difficult separation.

In addition, for being based on solvent-extracted recovery processing, because the scandium grade contained in nickel oxide ore is very micro, Direct treatment process liquid can make place capacity increase and have the difficulty in cost.

In addition, it is known that the actinides such as micro uranium, thorium often coexist in the rare earth elements such as scandium.Above-mentioned chelating The adsorption desorption behavior of uranium, thorium in resin is almost identical as scandium.That is, the side detached using above-mentioned chelating resin Method, is not only scandium and many actinides can also be adsorbed.Moreover, Acidic Liquid is passed through the feelings that chelating resin elutes Under condition, it is not only scandium and actinides is also eluted, the separation with scandium cannot be reached.

On the other hand, such as, it is desirable to use scandium as fuel cell etc. material in the case of, in order to ensure necessary performance Its quality with high-purity is required, therefore, it is considered that especially above-mentioned actinides should avoid.However, make not yet scandium with The method that these impurity elements headed by actinides efficiently separate.

Therefore, one kind is not found out also so far to be suitable for that scandium is made to efficiently separate with impurity element and industrialize from nickel oxide ore The method that ground recycles the scandium of high-purity.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 3-173725 bulletins.

Patent document 2：Japanese Unexamined Patent Publication 1-133920 bulletins.

Patent document 3：Japanese Unexamined Patent Publication 9-176756 bulletins.

Patent document 4：Japanese Unexamined Patent Publication 9-194211 bulletins.

Patent document 5：Japanese Unexamined Patent Publication 9-291320 bulletins.

Invention content

The subject that the invention solves

The present invention is to propose in view of the above fact, can be from its purpose is to provide a kind of recovery method of scandium Nickel oxide ore conveniently and efficiently recycles high-grade scandium.

The means to solve the problem

In order to solve the above problems, the inventors of the present invention, which are repeated, concentrates on studies.As a result, it has been found that being detached by chelating resin The scandium contained in nickel oxide ore, to using acid solution dissolving from scandium obtained from the hydroxide precipitation that scandium eluent obtains Acid dissoluting liquid implements solvent extraction, is roasted to the object containing scandium that the raffinate generated by the solvent extraction obtains, thus, it is possible to letters Just and it is efficiently obtained high-grade scandium, so far completes the present invention.That is, the present invention is provided such as with content.

(1) the first invention of the invention is a kind of recovery method of scandium, wherein it has：Process is leached, the process is in height The nickel oxide ore containing scandium is leached using sulfuric acid under warm high pressure and obtains leachate and leaching residue；Neutralize work Sequence, the process neutralizer is added in aforementioned leachate and obtain neutralization precipitation object and in and rear liquid；Vulcanization process, the process exist Vulcanizing agent is added in liquid and obtain liquid after nickel sulfide and vulcanization after aforementioned neutralization；Ion-exchange process, before the process is by making Stating liquid after vulcanization contacts to make with chelating resin the scandium after the vulcanization in liquid to be adsorbed in the chelating resin, obtains scandium eluent； Dissolution process, after which adds alkali in aforementioned scandium eluent and obtain scandium hydroxide sediment, in the scandium hydroxide It adds acid solution and carries out sour dissolving, thus obtain the acid dissoluting liquid of scandium；Solvent extraction step, the process make the acid dissolving of aforementioned scandium Liquid contact Neutral-neutral Extractants carry out the impurity element other than extraction and separation scandium, obtain the raffinate containing scandium；With scandium recovery process, the work Sequence adds oxalic acid to generate the salt of oxalic acid scandium in aforementioned raffinate, roasts the oxalic acid scandium salts and obtains scandium oxide.

(2) the second invention of the invention is a kind of recovery method of scandium, wherein in the first invention, aforementioned chelating resin It is using imino-diacetic acetic acid as the resin of functional group, foregoing ion exchanges process and includes：Absorption process, the process make aforementioned vulcanization Liquid contacts with aforementioned chelating resin and aforementioned scandium is made to be adsorbed in aforementioned chelating resin afterwards；Aluminium removing step, the process make 0.1N with Under sulfuric acid solution contacted with the chelating resin for having adsorbed scandium in preceding adsorption process, to removal in preceding adsorption process It is adsorbed in the aluminium of aforementioned chelating resin；Scandium elution procedure, the process make 0.3N less than the sulfuric acid solution and experience of 3N before It states the contact of the chelating resin after aluminium removing step and obtains aforementioned scandium eluent；With chromium removing step, which makes 3N's or more Sulfuric acid solution with undergo that the chelating resin after aforementioned scandium elution procedure contacts and remove be adsorbed in preceding adsorption process it is aforementioned The chromium of chelating resin.

(3) third of the invention invention is a kind of recovery method of scandium, wherein in first or second invention, aforementioned In solvent extraction step, the pH of the acid dissoluting liquid of aforementioned scandium is maintained into 1.0 or more and 2.5 ranges below, makes the acid of the scandium Lysate is contacted with aforementioned Neutral-neutral Extractants.

(4) the 4th invention of the invention is a kind of recovery method of scandium, wherein any one of first to third invention In the invention, aforementioned solvents extraction process includes：Extraction process, the process is by the acid dissoluting liquid of aforementioned scandium and containing in aforementioned Property extractant organic solvent mixing, be separated into organic solvent and raffinate after the extraction for having extracted the impurity element other than scandium； Cleaning process, the process mix 1.0moL/L or more and the acid solution of 5.0moL/L or less concentration with organic solvent after aforementioned extraction It closes, the organic solvent after being washed from organic solvent recycling scandium after the extraction；With back extraction process, the process is in aforementioned washing Strippant is added in organic solvent afterwards, impurity element is stripped from organic solvent after the washing and obtains anti-stripping agent.

(5) the 5th invention of the invention is a kind of recovery method of scandium, wherein in any one of first to fourth invention In the invention, in aforementioned dissolution process, sour dissolving is carried out by adding salpeter solution in aforementioned scandium hydroxide, to Obtain the nitric acid lysate of the scandium of the acid dissoluting liquid as scandium.

(6) the 6th invention of the invention is a kind of recovery method of scandium, wherein in any one of first to fourth invention In the invention, in aforementioned dissolution process, sour dissolving is carried out by adding hydrochloric acid solution in aforementioned scandium hydroxide, to Obtain the dissolving with hydrochloric acid liquid of the scandium of the acid dissoluting liquid as scandium.

(7) the 7th invention of the invention is a kind of recovery method of scandium, wherein in the 6th invention, is extracted in aforementioned solvents It takes in process, the chloride concentration of the dissolving with hydrochloric acid liquid of the aforementioned scandium obtained in aforementioned dissolution process is adjusted to 2.0moL/L Above and 6.0moL/L is hereinafter, make the dissolving with hydrochloric acid liquid of the scandium be contacted with aforementioned Neutral-neutral Extractants.

(8) the 8th invention of the invention is a kind of recovery method of scandium, wherein in any one of first to the 7th invention In the invention, aforementioned scandium recovery process includes：The sodium hydroxide of 5.0moL/L or more and 8.0moL/L or less concentration are added It is added in the aforementioned raffinate obtained in aforementioned solvents extraction process, the process for obtaining scandium hydroxide sediment；By what is obtained Scandium hydroxide sediment sulfuric acid or dissolving with hydrochloric acid, addition oxalic acid in the lysate obtained from being dissolved and obtain oxalic acid scandium The process of crystal；With the process being burnt into aforementioned oxalic acid scandium crystal.

The effect of invention

High-grade scandium can be conveniently and efficiently recycled according to the present invention from nickel oxide ore.Can especially it make In the case of containing actinides in the nickel oxide ore of raw material, actinides is efficiently separated from scandium.

Description of the drawings

Fig. 1 is an exemplary flow chart of the whole process of the recovery method for illustrating the scandium using the present invention.

Fig. 2 is the drafting of the relationship of chloride concentration when indicating scandium (Sc), uranium (U), the extraction yield of thorium (Th) and extraction Figure.

Specific implementation mode

In the following, specific embodiment (hereinafter referred to as " this embodiment party of the present invention is discussed in detail while with reference to attached drawing Formula "), but the present invention can be added not by any restriction of following implementation in the range of not changing the main points of the present invention It is appropriate to change to implement.

《1. the summary of the recovery method of scandium》

Fig. 1 is the flow chart of the recovery method of the scandium for illustrating present embodiment.The recovery method of the scandium, to sulfuric acid It is neutralized Deng the acid progress obtained leachate of leaching nickel oxide ore, is contained from as obtained from the neutralisation treatment Separation of Scandium, uranium and thorium in the hydroxide of scandium, uranium and thorium only recycle scandium to easy and efficient and high-purity.

Specifically, the recovery method of the scandium of present embodiment, has：Process S1 is leached, is used at high temperature under high pressure The acid such as sulfuric acid, which leaches the nickel oxide ore containing scandium, obtains leachate and leaching residue；Neutralization step S2 is soaking Go out in liquid and neutralizer is added and obtains liquid after neutralization precipitation object and neutralization；Vulcanization process S3 adds vulcanizing agent in liquid after the neutralization And obtain liquid after nickel sulfide and vulcanization；Ion-exchange process S4 makes after liquid is contacted with chelating resin to make vulcanization after vulcanization Scandium in liquid is adsorbed in chelating resin, then obtains scandium eluent；Dissolution process S5 adds alkali in scandium eluent and obtains scandium hydrogen After the sediment of oxide, the acid solution of hydrochloric acid or salpeter solution is added in the scandium hydroxide to obtain the acid dissolving of scandium Liquid；Solvent extraction step S6 makes the acid dissoluting liquid of scandium be contacted with Neutral-neutral Extractants so as to the impurity element other than extraction and separation scandium, Obtain the raffinate containing scandium；With scandium recovery process S7, so that the scandium contained by raffinate is generated oxalates, roast the oxalic acid scandium and obtain Scandium oxide.

Therefore, in the present embodiment, which is characterized in that when recycling and refining (purifying) scandium, combination ion is handed over (ion-exchange process) and solvent extraction (solvent extraction step) are changed, further before solvent extraction after ion exchange, by Scandium eluent generates the sediment containing scandium, dissolves the sediment with the acid solution of hydrochloric acid or nitric acid and obtains the acid dissoluting liquid of scandium (dissolution process).Then, solvent extraction is implemented to the acid dissoluting liquid, is added in the raffinate not being extracted in solvent extraction Oxalic acid and obtain oxalic acid scandium crystal.Based on this method, the impurity of uranium-bearing, thorium can be isolated with more high-grade, even right Contain more polymictic raw material in such as nickel oxide ore one kind, scandium that is easy and stablizing can be also carried out with compact equipment Recycle operation.

《2. each process of the recovery method about scandium》

Hereinafter, on one side referring to Fig.1 shown in flow chart, on one side be described in detail scandium recovery method each process.

(1) process is leached

In leaching process S1, the acid such as the nickel oxide ore containing scandium and sulfuric acid is packed into high-temperature pressurizing container together (autoclave) etc. passes through acid to nickel oxygen in the environment of 240 DEG C~260 DEG C high temperature and high pressure while implementing stir process Compound ore is leached, and the leaching slurry of residue is generated comprising leachate and leach.It should be noted that leaching process S11 As long as processing in is carried out according to previously known HPAL techniques, such as on the books in patent document 1.

Herein, as nickel oxide ore, the so-called laterite such as limonite and saprolife ore deposit can mainly be enumerated.It is logical Often, the nickel content of laterite is the 0.8 weight % of weight %~2.5, is hydroxide or silicon magnesia (magnesium silicate) mine containing form Object.Ingredient other than the valuable metals such as nickel, cobalt, scandium rich in aluminium, chromium, iron etc. in these nickel oxide ores.

In leaching process S11, the obtained leaching slurry being made of leachate and leaching residue is washed on one side, Leachate solid-liquid separation into nickeliferous, cobalt, scandium etc. and the leaching residue as bloodstone on one side.In the solid-liquid separation treatment, For example, after leaching slurry is mixed with cleaning solution, using the agglutinant by supplies such as agglutinant supply arrangements, pass through thickener (thickener) etc. solid-liquid separating equipments implement solid-liquid separation treatment.Specifically, first, leach slurry and be washed liquid dilution, Then, the leaching residue in slurry is concentrated as the sediment of thickener.In addition, in the solid-liquid separation treatment, preferably make The solid-liquid separation tanks multi-stag such as thickener connects to use, and is separated by solid-liquid separation while multistage washs leaching slurry.

(2) neutralization step

In neutralization step S2, adding neutralizer in the leachate obtained by above-mentioned leaching process S1 adjusts pH, Liquid after obtaining the neutralization precipitation object of impure element and neutralizing.Keep scandium, nickel etc. valuable by the neutralisation treatment in neutralization step S2 Metal, which is comprised in after neutralization, in liquid, makes most of impurity headed by iron, aluminium become neutralization precipitation object.

As neutralizer, known neutralizer can be used, for example, calcium carbonate, calcium hydroxide, sodium hydroxide can be enumerated Deng.

In the neutralisation treatment of neutralization step S2, it is preferable that inhibit the oxidation for the leachate isolated on one side, on one side by pH tune It saves to 1~4 range, is more preferably adjusted to 1.5~2.5 range.When pH is less than 1, it is possible to neutralize insufficient and nothing Liquid after method is separated into neutralization precipitation object and neutralizes.On the other hand, when pH is more than 4, it is possible to the impurity being more than headed by aluminium And the valuable metals such as scandium, nickel are also contained in neutralization precipitation object.

(3) vulcanization process

In vulcanization process S3, liquid addition vulcanizing agent after the neutralization that is obtained by neutralization step S2 is obtained nickel sulfide and Liquid after vulcanization.By the vulcanizing treatment in vulcanization process S3, nickel, cobalt, zinc etc. become sulphidisation, after scandium etc. is then comprised in vulcanization In liquid.

Specifically, in vulcanization process S3, to obtained neutralization after be blown into hydrogen sulfide gas, vulcanized sodium, sulphur hydrogen in liquid Change the vulcanizing agents such as sodium, generates impurity component few nickeliferous and cobalt sulfide (nickel cobalt mixed sulfides) and nickel concentration and stablized The liquid after low-level and vulcanization containing scandium etc..

In vulcanizing treatment in vulcanization process S3, using settling separation devices such as thickeners to nickel cobalt mixed sulfides Slurry carry out sedimentation separation processing, nickel cobalt mixed sulfides is separated and recovered by the bottom of thickener, on the other hand, make conduct Hydrorrhea stream after the vulcanization of aqueous solution ingredient and recycle.It should be noted that liquid is sulfuric acid solution after obtained vulcanization.

Herein, to liquid after the vulcanization that is obtained by the vulcanizing treatment in vulcanization process S3, aftermentioned oxalic acid, neutralization are directly added Agent and obtain scandium salts, oxide, by being roasted to it so as to obtaining solid oxidation scandium.But above-mentioned leachate, sulphur The concentration for the scandium for including in liquid after change is generally all very dilute, tens to 100mg/L or so, even in order to will be with more highly concentrated than scandium Other impurities existing for degree mode detach, it is also preferred that being carried out using means such as aftermentioned ion-exchange treatment, solvent extraction processing Concentration operation.

(4) ion-exchange process

In ion-exchange process S4, make liquid after the vulcanization that the wet type metallurgy by above-mentioned nickel oxide ore obtains Chelating resin is contacted, to make the scandium for including in liquid after the vulcanization be adsorbed in chelating resin, obtains the scandium after removal impurity component Eluent.

After curing in liquid, other than scandium as a purpose, also contain in the vulcanizing treatment in vulcanization process S3 not Aluminium, chromium and micro uranium, the thorium etc. to depend on the circumstances for curing and remaining in solution (liquid after vulcanization).In consideration of it, When liquid implements neutralisation treatment and generates hydroxide after vulcanizing to the acid solution, preferably removes these impurity and make scandium Concentration generates scandium eluent.

As the mode of ion-exchange process S4, it is not particularly limited, for example, an example as shown in Figure 1 is such, It preferably includes：Absorption process S41, liquid contacts chelating resin and scandium is made to be adsorbed in chelating resin after making vulcanization；Aluminium removing step S42 makes the 0.1N sulfuric acid solution Contact-sorptions below chelating resin of scandium, chelating tree is adsorbed in removal absorption process S41 The aluminium of fat；Scandium elution procedure S43, makes 0.3N or more and 3N sulfuric acid solution contacts below live through the chela of aluminium removing step S42 Resin and obtain scandium eluent；With chromium removing step S44, so that the sulfuric acid solution of 3N or more is contacted and live through scandium elution procedure The chelating resin of S43 removes the chromium that chelating resin is adsorbed in absorption process S41.

[absorption process]

In absorption process S41, liquid contacts chelating resin and scandium is made to be adsorbed in chelating resin after making vulcanization.It is set as chelating Fat is not particularly limited, for example, it is preferable to use using imino-diacetic acetic acid as the resin of functional group.

Herein, during the chelating resin absorption scandium in absorption process S41, the pH ranges of solution are lower, nickel oxide The adsorbance for the impurity for including in ore is fewer.Therefore, by the way that the liquid in the alap regions pH is passed through chelating resin, from And absorption of the impurity to chelating resin can be inhibited.But when the pH of solution is less than 2, it is possible to be not only the absorption of impurity It measures and the adsorbance of scandium can also tail off.

[aluminium removing step]

In aluminium removing step S42,0.1N sulfuric acid solution contacts below is preferably made to have adsorbed scandium in absorption process S41 Chelating resin, to remove the aluminium adsorbed on the chelating resin.

During the aluminium adsorbed on removing chelating resin, it is preferable that the pH of sulfuric acid solution is maintained 1 or more and 2.5 Range below more preferably maintains 1.5 or more and 2.0 ranges below.When the pH of sulfuric acid solution is less than 1, it is possible to no Only aluminium and scandium can be also removed from chelating resin.On the other hand, when the pH of sulfuric acid solution is more than 2.5, it is possible to which aluminium cannot It is suitably removed from chelating resin.

[scandium elution procedure]

In scandium elution procedure S43, preferably by making 0.3N live through aluminium less than the sulfuric acid solution contact of 3N Except the chelating resin of process S42, to obtain scandium eluent.

During obtaining scandium eluent, preferably by the equivalent concentration of the sulfuric acid solution used as eluent (regulation Degree) ranges of the 0.3N less than 3N is maintained, more preferably maintain equivalent concentration of the 0.5N less than the range of 2N. When the equivalent concentration of sulfuric acid solution is in 3N or more, it is possible to be not only scandium and chromium can be also comprised in scandium eluent. On the other hand, when the equivalent concentration of sulfuric acid solution is less than 0.3N, it is possible to which scandium is not removed suitably from chelating resin.

[chromium removing step]

In chromium removing step S44, the sulfuric acid solution of 3N or more is preferably made to contact the chelating for living through scandium elution procedure S43 Resin, to remove the chromium adsorbed on chelating resin.

During the chromium adsorbed on removing chelating resin, when the equivalent concentration of the sulfuric acid solution used as eluent When being down to 3N or less, chromium is not removed suitably from chelating resin sometimes.It is preferable therefore that the sulfuric acid solution of 3N or more is made to contact Chelating resin is handled.

[iron removing step]

In addition, though it is not shown, but contain iron as impurity from the leachate that nickel oxide ore obtains sometimes.This feelings Under condition, it is preferable that before aluminium removing step S42, make the equivalent concentration of the sulfuric acid solution than will be used in aluminium removing step S42 The small centinormal 1 sulfuric acid solution Contact-sorption chelating resin of scandium, to remove the iron adsorbed on the chelating resin.

During the iron adsorbed on removing chelating resin, the pH of sulfuric acid solution is preferably maintained into 1 or more and 3 or less Range.When the pH of sulfuric acid solution is less than 1, it is possible to be not only iron and scandium can be also removed from chelating resin.It is another Aspect, when the pH of sulfuric acid solution is more than 3, it is possible to which iron is not removed suitably from chelating resin.

＜ scandiums eluent adsorbs ＞ again to chelating resin

In addition, though mode is not essential, it is preferred that the scandium eluent for implementing to make is adsorbed to chelating resin again Processing.

Specifically, adding neutralizer in the scandium eluent obtained in scandium elution procedure S43, pH is preferably adjusted to 2 Above and 4 ranges below, the range (process S101) below of 2.7 or more and 3.3 being more preferably adjusted to centered on pH3, Thereafter, it adds reducing agent (process S102) and further adds sulfuric acid so that pH is preferably adjusted to 1 or more and 2.5 models below It encloses, 1.7 or more be more preferably adjusted to centered on pH2 and 2.3 ranges (process S103) below.Scandium elution is obtained based on this Liquid after the pH of liquid is adjusted, liquid carries out the processing in above-mentioned ion-exchange process S4 again after being adjusted with the pH.

Thus, repeat ion-exchange process S4 by the scandium eluent made is adsorbed in chelating resin again In processing, so as to further improve recycling scandium grade.It can also enough reduce from scandium eluent Separation of Scandium mistake Reagent cost, equipment scale in journey.

During scandium eluent adsorbs again to chelating resin, it is preferable that in the addition (process S102) of reducing agent, with Silver/silver chloride electrode as the value of the oxidation-reduction potential (ORP) of reference electrode be maintained at higher than 200mV and 300mV with Under range carry out.When ORP is 200mV or less, it is precipitated at fine solid at branch sometimes from the sulphur of the vulcanizing agent of addition Body.In this case, just become in filtration treatment after curing and block filter cloth and so that solid-liquid separation efficiency is deteriorated and cause to produce Property decline cause, and then as during being passed through liquid again to chelating resin in resin tower occur block, liquid flowing Segregation and the cause that uniform liquid is passed through etc. cannot be carried out.On the other hand, when ORP is more than 300mV, it is possible to remain Be adsorbed in resin and scandium is hindered to adsorb the problems such as such as iron ion.

As the neutralizer added to scandium eluent, known neutralizer can be used, for example, calcium carbonate can be enumerated Deng.In addition, about the reducing agent added after pH is adjusted, known reducing agent can be also used, for example, vulcanization can be enumerated The vulcanizing agents such as hydrogen, vulcanized sodium, sulfur dioxide gas, hydrazine, metallic iron etc..

When so that scandium eluent is adsorbed in chelating resin again, as the chelating resin, it can reuse and use It crosses, new chelating resin can also be used.If from the viewpoint of the pollution for preventing impurity, preferably reuses and live through chromium Except the chelating resin or the new chelating resin of use of process S44.In particular, living through chromium removing step S44's by reusing Chelating resin can not only prevent the pollution of impurity, and can inhibit the usage amount of chelating resin.

The purifying ＞ of ＜ scandium eluents

In addition, to the scandium eluent obtained by scandium elution procedure S43, can again carry out in scandium elution procedure S43 Processing, i.e., the processing that the scandium eluent made for the chelating resin for living through aluminium removing step S42 is in contact with it.Such as This place, by repeating scandium elution procedure S43 with scandium eluent, so as to improve the concentration of scandium eluent.

Although repeating, scandium S43 number of elution procedure is more, and the concentration of the scandium of recycling is higher, crosses after being repeated several times and recycles Scandium concentration rise degree taper into.Therefore, industrially, it is preferable that the number for repeating scandium elution procedure S43 is 8 times Left and right below.

(5) dissolution process

Then, following processing in this way is carried out, i.e., then above-mentioned ion-exchange process S4 is arranged dissolution process S5, scandium is made to wash The scandium that de- liquid includes generates sediment and is detached with impurity, further dissolves the sediment with acid solution, generates and is used for follow-up work The initial liquid of solvent-extracted extraction of sequence.

The method for concentration of scandium in dissolution process S5, which is the sediment of generation scandium, makes the method that it is detached with impurity, can make The method neutralized with hydroxide.

[hydroxide neutralization]

In the hydroxide neutralisation treatment to scandium eluent, by being eluted to the scandium obtained in above-mentioned ion-exchange process S4 Liquid adds neutralizer to implement neutralisation treatment, to liquid after the neutralization of hydroxide precipitation and impurity component of the generation comprising scandium.

As the neutralizer for making an addition to scandium eluent, known neutralizer can be used, for example, niter can be enumerated The alkali such as ash, sodium hydroxide.Wherein, in the case where scandium eluent is sulfuric acid solution, it is preferable to use the conducts such as sodium hydroxide Neutralizer, if because the neutralizer of the ingredient containing Ca can generate gypsum.

For the pH after addition neutralizer, it is not particularly limited, is preferably adjusted to 8 or more and 9 ranges below.When pH is small When 8, it is possible to neutralize it is insufficient, cannot fully with precipitated form recycle scandium eluent in scandium.On the other hand, when pH is super When 9, because the usage amount of neutralizer can be increased, from the point of view of the point of cost increase not preferably.

In addition, in order to reduce Iron grade, 2 grades of neutralizations of progress are more effective, i.e., are carried out during hydroxide neutralisation treatment Neutralization for only making the first order that iron precipitates, will carry out the neutralization of the second level again after the filtering of obtained sediment.

[dissolving based on acid]

Then, in the present embodiment, to the scandium hydroxide sediment obtained by hydroxide neutralisation treatment, addition acid is molten Liquid specifically adds any acid solution of nitric acid or hydrochloric acid, thus dissolves the sediment, generate the acid dissoluting liquid of scandium. In the recovery method of the scandium of present embodiment, using the acid dissoluting liquid of the obtained scandium as subsequent handling solvent extraction step S6 In solvent extraction processing process object (extracting initial liquid).

Specifically, as the acid solution for dissolving scandium hydroxide sediment, it is right using salpeter solution The concentration of the salpeter solution, is not particularly limited, preferably 2.0moL/L or more and 5.0moL/L ranges below, more preferably 3.0moL/L or more and 4.0moL/L ranges below.

In addition, in the case where using hydrochloric acid solution as acid solution, to the concentration of the hydrochloric acid solution, do not limit especially It is fixed, as long as the concentration suitable for the solvent extraction processing in aftermentioned solvent extraction step S6.

In addition, during carrying out sediment dissolving based on acid solution, the preferred solubility in obtained sediment Nearby dissolved.Accordingly, because arbitrary concentration can be redissolved into after solid is precipitated, so can arbitrarily select scandium dense Degree, from the liquid measure that can not only reduce in subsequent handling solvent extraction step S6 and the viewpoint that equipment scale can be reduced It sees, it is industrially extremely preferred.

So, in the present embodiment, dissolution process S5 is designed by then ion-exchange process S4, so as to big Impurities in scandium eluent are removed to amplitude, ion-exchange process S4, subsequent handling solvent extraction step S6 phases can be mitigated The operation quantity of pass.In addition, because the concentration for the solvent-extracted initial liquid of extraction can be adjusted arbitrarily, it is based on solvent The reduction for the equipment investment that the diminution of the equipment scale of extraction process S6 is brought, the stabilisation of initial liquid concentration, can be further Operation is set to stabilize.

(6) solvent extraction step

In solvent extraction step S6, scandium hydroxide is dissolved with hydrochloric acid or salpeter solution by making in above-mentioned dissolution process S5 Obtained from acid dissoluting liquid (extracting initial liquid) the contact Neutral-neutral Extractants of scandium carry out solvent extraction processing, to be contained The organic solvent of impurity and the raffinate containing scandium are extracted.

Solvent extraction processing in this way, can efficiently and effectively detach the impurity other than scandium with scandium, Neng Gouti The purity of high scandium.Particularly, in the present embodiment, because being extracted using the acid dissoluting liquid of the scandium obtained as described above as solvent The object of processing is taken, so extractant more effectively extracting impurities can be utilized.

It to the mode of solvent extraction step S6, is not particularly limited, for example, an example as shown in Figure 1 is such, preferably Have：The acid dissoluting liquid of scandium and the organic solvent containing Neutral-neutral Extractants are obtained by mixing organic after extracting by extraction process S61 Solvent and raffinate；Cleaning process S62 mixes hydrochloric acid or the salpeter solution of normal concentration to divide after the extraction in organic solvent From and recycle and be extracted into the scandium of extractant；With back extraction process S63, strippant is added in organic solvent after washing, From being stripped impurity element in organic solvent after the washing.

[extraction process]

In extraction process S61, the acid dissoluting liquid of scandium and the organic solvent containing Neutral-neutral Extractants are mixed, selectively extracted Take the impurity element other than scandium.By the extraction processing, the extraction that the purity of organic solvent and scandium containing impurity is enhanced is obtained Extraction raffinate.

Various Neutral-neutral Extractants are known, there is no particular limitation as to it, it is preferable to use phosphorous extractant, tool TBP (TRI N BUTYL PHOSPHATE) etc. is used for body.In the case of using TBP as extractant, dissolved for the acid of nitric acidic Liquid can extract in its solution the uranium and thorium for including, them is made efficient to be detached with scandium.In addition, the acid for acidity of hydrochloric acid is molten Liquid is solved, the uranium for including in its solution can be mainly extracted, so that uranium is efficient detached with scandium.

During property extractant in use carries out extraction processing, preferably hydrocarbon system organic solvent etc. is used to dilute the extractant To use.For example, in the case of using above-mentioned TBP as Neutral-neutral Extractants, if phase separation when in view of extraction, back extraction Etc. if, the concentration of the TBP in organic solvent is preferably 10 volume % or more and 50 volume % hereinafter, especially more preferable For the 15 volume % or more and 25 volume % or less before and after 20 volume %.

In addition, for extraction when scandium acid dissoluting liquid and organic solvent volume ratio, be not particularly limited, it is preferable that Relative to the mole of the metal in the acid dissoluting liquid of scandium, keep organic solvent mole below as 0.4 times or more and 1.0 times Range.

Herein, in extraction processing, preferably the pH of the acid dissoluting liquid of scandium is adjusted and maintains 1.0 or more and 2.5 or less Range.When the pH of the acid dissoluting liquid of the scandium as extraction processing object is less than 1.0, in the case of containing uranium in the solution, The extraction of the uranium can hardly be carried out, extraction and separation effect is possible to be remarkably decreased.In addition, the acidity of the acid dissoluting liquid of scandium is spent By force, there are the hidden danger that equipment is easily corroded.

On the other hand, it in extraction processing, when the pH of the acid dissoluting liquid in scandium is more than in the state of 2.5, generates sometimes The hydroxide of scandium and as occur covering (clad) cause, there are the hidden danger of operation difficulty.

The pH of acid dissoluting liquid as the scandium in extraction processing is more preferably adjusted and is maintained 1.5 or more and 2.0 is below Range, thereby, it is possible to uranium that is more effective and more efficiently including in extraction solution.

In addition, in extraction processing, the acid dissoluting liquid as scandium uses acidity of hydrochloric acid solution (the dissolving with hydrochloric acid liquid of scandium) In the case of, the chloride concentration (T-Cl concentration) of acidity of hydrochloric acid solution when extraction, preferably 2.0moL/L or more.So will Chloride concentration is adjusted to 2.0moL/L or more to implement extraction processing, can improve the extraction yield of uranium.

On the other hand, the upper limit value of chloride concentration, preferably 6.0moL/L or less.When the chloride of acidity of hydrochloric acid solution When concentration is more than 6.0moL/L, the chlorides such as iron ion coexisted will become supersaturated with and crystallization is caused to be precipitated, and exist to form packet Layer and interfere the hidden danger of operation.

About the adjusting of the chloride concentration in acidity of hydrochloric acid solution, for example, it is preferable to add the alkali such as sodium chloride, potassium chloride gold The salt of category carries out.It should be noted that for example, when using hydrochloric acid come when adjusting chloride concentration, the acid of acidity of hydrochloric acid solution Property spend it is strong, it is possible to pH can be disengaged to side more smaller than above-mentioned preferred range (pH1.0 or more and 2.5 or less), and having can The extraction and separation effect of uranium can be reduced.

In addition, as the temperature condition in extraction processing, there is no particular limitation, based on extraction efficiency in terms of from the point of view of, It is preferred that relative temperature is higher, but it is excessively high if, there are the hydrochloric acid for constituting acid dissoluting liquid, nitric acid volatilization or the dangerous feelings such as on fire Condition.It is preferable therefore that being probably set in 40 DEG C or more and 50 DEG C of ranges below to carry out.

[cleaning (washing) process]

In above-mentioned extraction process S61, in the case of scandium coexists microly in the organic solvent of extracting impurities, right Extract liquor is implemented before back extraction, it is preferable that implements cleaning (washing) processing for the organic solvent (organic phase), scandium is made to be separated to Water phase recycles (cleaning process S62) by extractant.

Cleaning process S62 arranged so washs organic solvent, makes the micro scandium separation for being extracted agent extraction, It thus enables that scandium is separated in cleaning solution, the rate of recovery of scandium can be further increased.

To the solution (washing solution) used in cleaning, there is no particular limitation, for example, hydrochloric acid solution, sulphur can be used Acid solution, salpeter solution etc., but to be purified together with the raffinate after extraction by the cleaning solution that cleaning is recycled and be used for scandium Recycling.Therefore, in cleaning, it is preferable to use with the salpeter solution of the identical class of liquids of the extraction acid dissoluting liquid of stoste, that is, scandium or Hydrochloric acid solution is as washing solution.That is, lysate for acidity of hydrochloric acid, it is preferable to use hydrochloric acid system washing solution, And lysate for nitric acidic, it is preferable to use nitric acid system washing solution.In addition, from the hydrolysis for preventing pH risings from causing scandium From the viewpoint of, it is also preferred that using these washing solution.It is further possible to be formed using soluble sulfate is added in water Liquid.

To washing the concentration of solution, it is not particularly limited, preferably 1.0moL/L or more and 5.0moL/L ranges below. More specifically, for example, as washing solution use such as salpeter solution in the case of, preferably 2.0moL/L or more and 5.0moL/L or less concentration ranges, more preferably 3.0moL/L or more and 4.0moL/L or less concentration ranges.

Washing series (number) as cleaning can be according to neutrality because additionally depending on the type of impurity element, concentration Extractant, extraction conditions suitably change.For example, in organic phase (O) and in the case of being comparably O/A=1 of water phase (A), lead to Cross and be set as 3~5 grades or so of series, the scandium being extracted in organic solvent can be detached until less than analytical equipment detection Lower limit.

[back extraction process]

In being stripped process S63, impurity element is stripped from the organic solvent for having extracted impurity element.Specifically, In back extraction processing, addition stripping solution (being stripped initial liquid) is mixed in the organic solvent containing extractant, by This generates the reaction opposite with the extraction processing in extraction process S61 to be stripped impurity element, obtains containing the impurity element Back extraction after liquid.

As described above, in the extraction processing carried out for the acid dissoluting liquid of the scandium in extraction process S61, as extraction Agent is using the Neutral-neutral Extractants such as TBP so as to selectively extracting impurities element.As a result, from make the impurity element from containing extractant From the perspective of organic solvent efficiently and effectively detaches and makes extractant regeneration, as stripping solution, for example, it is preferable to use Pure water.

It should be noted that in above-mentioned cleaning process S62, cleaning treatment is being implemented to the organic solvent containing extractant In the case of, stripping solution can be equally added to the extractant after cleaning and is mixed, and back extraction processing is thus carried out.

So the stripping solutions such as pure water are added to the extractant after extraction or the extractant after cleaning to be stripped Processing makes the Neutral-neutral Extractants after separation impurity element, can be again as using in the extraction processing in extraction process S61 Extractant is reused.

＜ scandium recovery process ＞

Then, in scandium recovery process S7, scandium is recycled from the raffinate containing scandium obtained by solvent extraction step S6. In scandium recovery process S7, after so that scandium contained in raffinate is generated salt, by roasting the solid scandium salts, so as to generate oxygen Change scandium and recycles scandium.

Specifically, a scandium recovery process S7 example as shown in Figure 1 is such, have：Oxalic acid salt chemical engineering sequence S71, Oxalic acid is added in the raffinate obtained in solvent extraction step S6 and obtains oxalic acid scandium crystal；With calcining process S72, to oxalic acid Scandium crystal is burnt into.

Especially in the case where using acidity of hydrochloric acid solution (the dissolving with hydrochloric acid liquid of scandium) as scandium lysate, by using The solvent extractions of Neutral-neutral Extractants is handled, and uranium is mainly extracted, and the separation of thorium and scandium has slightly insufficient.But its it In processing afterwards, by obtained raffinate add oxalic acid make scandium precipitation generate oxalates, can with do not form oxalates The thorium of precipitation efficiently separates.

[oxalic acid salt chemical engineering sequence]

Oxalic acid salt chemical engineering sequence S71 is the process for the precipitation for generating scandium as described above, in this process, by solvent extraction Oxalic acid is added in the raffinate (liquid after extraction) that process S6 is obtained to be made oxalic acid scandium white crystals be precipitated as solid, precipitates and divide From.

It to the additive amount of oxalic acid, is not particularly limited, it is preferable that addition makes the scandium in raffinate that institute be precipitated in the form of oxalates 1 times or more and 2.5 times of amounts below of the equivalent needed, more preferably 1.05 times or more and 2.0 times of amounts below.When its additive amount When 1 times of required equivalent is precipitated in deficiency, it is possible to scandium whole in raffinate cannot be recovered to.On the other hand, work as additive amount When more than 2.5 times of equivalent needed for precipitation, oxalic acid scandium solubility increase causes scandium to be redissolved and the rate of recovery declines or for decomposing The usage amount of the oxidant of the sodium hypochlorite class of superfluous oxalic acid increases.

It should be noted that making scandium that required equivalent be precipitated in the form of oxalates, oxalic acid and scandium following formula can be defined as (i) amount (multiple) relative to scandium when reaction generates oxalic acid scandium is carried out shown in like that.

The pH of raffinate when reacting oxalic acid salinization, is not particularly limited, for example, in the feelings using nitric acidic solution Under condition, preferably pH be 0 or more and 2 or less Zuo You range, before and after further preferably 1.When being less than 0 when pH is too low, have Possible oxalic acid scandium solubility increases, and the scandium rate of recovery declines.On the other hand, when pH is more than 2, the also shape of impurity contained in raffinate At precipitation, become the reason of scandium purity declines.

In addition, using acidity of hydrochloric acid solution in the case of, preferably by pH be set as 0 or more and 0.5 or less Zuo You range. When being less than 0 when pH is too low, it is possible to which oxalic acid scandium solubility increases, and the scandium rate of recovery declines.In addition, though as described above by Chloride concentration can be adjusted using the salt of the alkali metal such as sodium chloride, potassium chloride, but also leads to the sodium, the potassium that are attached to oxalic acid scandium Increase, progress water washing is needed to remove them.In addition, from the viewpoint of preventing pH from excessively rising and cause contamination precipitation, make 0.5 is preferably set to hereinafter, than using low under nitric acidic solution conditions with the pH under acidity of hydrochloric acid solution conditions.

It herein, can also be to being obtained by solvent extraction step S6 before the oxalic acid salinization processing in oxalic acid salt chemical engineering sequence S71 The raffinate containing scandium arrived implements neutralisation treatment, generates the sediment of scandium, to remove impurity.

Specifically, the sodium hydroxide for adding normal concentration to the raffinate obtained by solvent extraction step S6 (neutralizes Agent), generate scandium hydroxide sediment (raffinate neutralisation treatment).Thereafter, to obtain scandium hydroxide sediment addition sulfuric acid or Hydrochloric acid dissolves sediment, obtains scandium lysate (dissolving with hydrochloric acid processing).

Concentration to the sodium hydroxide added in raffinate neutralisation treatment, is not particularly limited, preferably 5moL/L or more And 8moL/L ranges below.Because the pH of solution (raffinate) can generate scandium hydroxide as precipitation in the state of 8 or more Both object, if consider sediment generation and inhibit superfluous sodium hydroxide, it is preferable that the pH of raffinate can be made 8 or more and 9 The mode of range below adds the sodium hydroxide.Based on the point, the concentration of the sodium hydroxide based on addition is in 5moL/L or more And 8moL/L ranges below, it is able to efficiently generate scandium hydroxide sediment.

To so implementing scandium lysate obtained from neutralisation treatment, above-mentioned oxalic acid salinization processing (oxalates can be carried out Chemical industry sequence S71).Thereby, it is possible to further recycle the scandium of high-purity.

[calcining process]

It in calcining process S72, is washed with water by the sediment of the obtained oxalic acid scandiums of oxalic acid salt chemical engineering sequence S71, dry, roasting It burns, thus generates scandium oxide.By so implementing calcination process, scandium can be recycled in the form of extremely high-grade scandium oxide.

It to the condition of the calcination process in calcining process S72, is not particularly limited, as long as example, by the oxalic acid after drying Scandium sediment is put into tube furnace and is heated 2 hours or so under the conditions of about 900 DEG C.It should be noted that industrially, using The continuous ovens such as rotation stove can be dried and roasted with same device, therefore preferably.

Embodiment

Hereinafter, the present invention is described in more detail by embodiment, but the present invention is not by any restriction of these embodiments.

《Embodiment 1》

[leaching process S1]

First, nickel oxide ore is packed into autoclave together with the concentrated sulfuric acid, it is small after 1 under 245 DEG C of temperature condition Shi Shengcheng contains the leaching slurry of the valuable metals such as scandium, nickel, and the leaching of various valuable metals is contained from the slurry solid-liquid separation Liquid and leaching residue.

[neutralization step S2]

Then, calcium carbonate (neutralizer) is added in the leachate being isolated implement neutralisation treatment.Pass through the neutralization Processing obtains liquid and the neutralization precipitation containing the most impurity headed by aluminium after the neutralization containing valuable metals such as scandium, nickel Object.

[vulcanization process S3]

Then, it is blown into hydrogen sulfide gas (vulcanizing agent) into liquid after obtained neutralization, nickel, cobalt, zinc is made to become sulfide, with It is detached as liquid after the vulcanization of the liquid after the vulcanizing treatment.

[ion-exchange process S4]

(absorption process S41)

Then, calcium hydroxide being added in liquid after the vulcanization of resulting separation, the pH of solution is adjusted to 1.6 as neutralizer. Further, it is not contained in the liquid after addition calcium hydroxide or its content is also denier containing element to illustrate Behavior, add reagent for the element of part, obtained the absorption stoste formed shown in the following table 1.

Table 1

The absorption stoste formed shown in table 1 is passed through and is filled with using imino-diacetic acetic acid as the chelating resin of functional group (ProductName：Diaion CR11 (ダ イ ヤ イ オ Application CR11), Mitsubishi chemical Co., Ltd's system) pillar.It should be noted that The amount of resin of pillar is set as 40 liters, is passed through liquid with 5.3 liters of flow per minute and makes SV=8, is passed through liquid until 2400 liters (bed volume (Bed Volume)：BV=2400/40=60).The liquid temperature to liquid when being passed through liquid is set as 60 DEG C.

(aluminium removing step S42)

Then, 800 liters of the sulfuric acid solution of concentration 0.1N is passed through by adsorption treatment with the flow of 27 liters (SV=40) per minute Chelating resin afterwards.What is be discharged from column remains the cleaning solutions of many aluminium as aluminum cleaning solution storage, by part sample preparation with ICP into Row analysis.As a result, assay value is Ni：7mg/L、Mg：1mg/L、Mn：4mg/L、Fe：1mg/L、AL：84mg/L、Sc：3mg/L. It should be noted that the assay value of Cr, Ca are less than measurable lower limit.

(scandium elution procedure S43)

Thereafter, 400 liters of the sulfuric acid solution of concentration 1N is passed through by chelating resin with the flow of 80 liters (SV=40) per minute.From The eluent of pillar discharge stores as scandium eluent and analyzes part sample preparation.The following table 2 shows the analysis of scandium eluent As a result.It should be noted that measurable lower limit is not analyzed or is less than in the "-" expression in table.

Table 2

(chromium removing step S44)

Then, 80 liters of the sulfuric acid solution of concentration 3N is passed through by chelating resin with the flow of 2.6 liters (SV=40) per minute.From The cleaning solution of pillar discharge stores as chromium cleaning solution and analyzes part sample preparation.As a result, assay value is Fe：2mg/L、 Cr：30mg/L.In addition, the assay value of Ni, Mg, Mn, AL, Ca, Sc are less than measurable lower limit.

[dissolution process S5]

Then, sodium hydroxide is added in the scandium eluent formed shown in table 2 and pH is maintained 8~9, generates scandium Hydroxide precipitates.Addition salpeter solution is precipitated to the hydroxide to dissolve, and obtains chelating eluent hydroxide dissolving Liquid (the nitric acid lysate of scandium).The following table 3 shows the analysis result of the composition of lysate.In addition, in table "-" expression do not analyze or Less than measurable lower limit, for example, the assay value of Mg, Cr, Mn, Ca are less than measurable lower limit.

Table 3

[solvent extraction step S6]

(extraction process S61)

Then, the 103 liters of conducts of the nitric acid lysate of the scandium formed shown in table 3 initial liquid is extracted to carry out at solvent extraction Reason.Specifically, by the initial liquid of the extraction, with TRI N BUTYL PHOSPHATE (trade name used as Neutral-neutral Extractants：TBP is big by eight Chemical Co., Ltd. system) and as organic solvent TecleanN20 (テ ク N20, JX days mine days of リ ー Application stone Co. Ltd. systems) 20.6 liters of mixing of organic solvent of 50 volume % are adjusted to, are stirred at room temperature 60 minutes.It is handled, is obtained by the solvent extraction Liquid (raffinate) after extraction organic phase and extraction containing the impurity except scandium.It should be noted that do not have not only when the extraction There is the phase separation after forming covering and standing to carry out also rapidly.

Analyze the composition for the various elements for including in obtained extraction organic phase.Include in calculating extraction organic phase is various The percentage of the obtained value of object amount of each element contained in stoste before the object amount of element divided by extraction, as extraction yield (%), is as a result shown in the following table 4.It should be noted that measurable lower limit is not analyzed or is less than in the "-" expression in table.

Table 4

According to the result of extraction yield shown in table 4 it is found that being handled by the solvent extraction in extraction process S61, before extraction The most of scandium residual for including in stoste in liquid (raffinate), is not extracted after the extraction.In addition, uranium, thorium impurities element with High ratio is extracted to extraction organic phase.In addition, understand to be practically free of in extracting organic phase aluminium, nickel, magnesium, chromium, manganese, calcium, Cobalt, copper, Zn-ef ficiency.

(cleaning (washing) process S62)

Then, relative to 20.6 liters of the organic solvent (extraction organic phase) obtained in extraction process S61, to compare (O/A) it is 0.3 ratio, with the salpeter solution of 6.2 liters of amount melting concn 3moL/L, stirs 10 minutes, cleaned and (washed It washs).Thereafter, water phase is stood and detaches, 6.2 liters of the new salpeter solution by organic phase again with concentration 3moL/L, which mixes, to be repeated to wash It washs, similarly detaches water phase.Repeat such washing operation totally 3 times.

Analyze the composition for the various elements for including in the cleaning solution after the washing operation.Include in calculating cleaning solution is various The percentage of the object amount of element divided by the obtained value of object amount in the extraction organic phase obtained by extraction process S61, is made For the rate of recovery (%), it is as a result shown in the following table 5.It should be noted that the "-" expression in table is not analyzed or less than under measurable Limit.

Table 5

Organic phase is extracted by so 3 times washings, so as to the micro scandium point that will be extracted in organic solvent From to water phase, the scandium concentration in organic solvent can be made to deteriorate to less than the level of 10mg/L.

(back extraction process S63)

Then, pure water is mixed into the ratio compared to O/A=1/0.3 in the extraction organic phase after washing, is stirred 20 minutes, It stands, the organic phase (organic solvent) after separation back extraction and phase of turning one's coat (liquid after back extraction).

[scandium recovery process S7]

(oxalic acid salt chemical engineering sequence S71)

Then, to liquid (raffinate) after the extraction that is obtained in above-mentioned solvent extraction step S6, addition is calculated as phase with calculation amount It is molten for 2 times of 2 hydrate of oxalic acid (Mitsubishi Gas society (ガ ス societies of the Mitsubishi) system) crystal for the scandium amount for including in the raffinate Solution stirs 60 minutes, mixing, generates the white crystalline precipitation of oxalic acid scandium.

(calcining process S72)

Then, obtained oxalic acid scandium sediment is filtered under diminished pressure, after pure water, under 105 DEG C of temperature conditions It is 8 hours dry.Then, the oxalic acid scandium after drying tube furnace is put into maintain at 850 DEG C~900 DEG C implementation roastings (firing) Reason, obtains scandium oxide.

Obtained scandium oxide is analyzed using ICP Atomic Emission Spectrophotometer method, investigated by above-mentioned solvent extraction processing and The slip of the thorium (Th) as impurity in the scandium oxide of recycling.It should be noted that the slip about thorium, be with without Above-mentioned solvent extraction processing and the thorium amount in the scandium oxide that is obtained by calcination process is used as benchmark, calculating is to by ion-exchange process The scandium eluent that S4 is obtained carries out the slip of the thorium of the nitric acid lysate of scandium made of the processing of dissolution process S5.By scandium oxide In thorium grade and the result of calculation of slip be shown in the following table 6.

Table 6

According to result shown in table 6 it is found that by above-mentioned scandium recovery process, can almost remove as impurity Thorium, can be with scandium oxide (Sc₂O₃) form scandium is recycled with high purity.

《Embodiment 2》

In a manner of similarly to Example 1, nickel oxide ore is leached with sulfuric acid, liquid after obtained vulcanization is led to Enter chelating resin, adds sodium hydroxide in the scandium eluent eluted from chelating resin and obtain the hydroxide precipitation of scandium.

Then, in example 2, to the hydroxide precipitation addition hydrochloric acid and sodium chloride of obtained scandium, dissolving obtains Acidity of hydrochloric acid solution (the dissolving with hydrochloric acid liquid of scandium).The ingredient of part is added with dosage form in the acidity of hydrochloric acid solution, point The initial liquid of extraction formed shown in the following table 7 is not prepared, using them as initial liquid A~H.

Table 7

* unit is [g/L], is [mg/L] to Th and U.

* oxidation-reduction potential (ORP) [mV] is using Ag-AgCl electrodes as reference electrode.

Then, the initial liquid of the extraction formed shown in E~H of table 7 is respectively taken out into 21mL respectively, is mixed into thereto containing 1 body The organic solvent 7mL of the TBP as Neutral-neutral Extractants of product % is poured into stir 15 minutes under room temperature state in beaker and is implemented extraction Take processing.It after stirring, stands, organic solvent (extractant) and raffinate after being divided into extraction with separatory funnel utilize ICP points It does not analyze it.

Herein, chloride concentration when extraction (T-Cl) is according to scandium, aluminium, iron, uranium, the respective assay value of thorium and in hydrochloric acid The Cl amounts for including in the hydrochloric acid and sodium chloride that are added when the total and adjusting for the Cl amounts that form present in acid solution calculates It calculates.

The composition of the raffinate handled by the solvent extraction of acidity of hydrochloric acid solution is shown in the following table 8.It needs to illustrate , in table 8, the chloride concentration (T-Cl) when by the extraction is shown together as the concentration (moL/L) in raffinate.

Table 8

* unit is [g/L], is [mg/L] to Th and U.

* oxidation-reduction potential (ORP) [mV] is using Ag-AgCl electrodes as reference electrode.

As shown in table 8, extracted using the solvent that E~H acidity of hydrochloric acid solution (extracting initial liquid) in the present embodiment 2 carries out It takes, it is thus identified that uranium is effectively extracted.

In addition, calculating respective object amount gained in the scandium in above-mentioned organic solvent, uranium, the object amount of thorium divided by the initial liquid of extraction The percentage of the ratio (object amount in the initial liquid of object amount/extraction in organic solvent) arrived, the following table 9 is shown in as extraction yield (%) And Fig. 2.In addition, Fig. 2 is the drafting figure of the relationship for the extraction yield relative to chloride concentration for indicating each element.

Table 9

As shown in table 9 and Fig. 2, it is thus identified that if the T-Cl (chloride concentration) in acidity of hydrochloric acid solution is 2.16moL/L, Then the extraction yield of uranium is 62.1%, if T-Cl is 2.37moL/L, the extraction yield of uranium reaches 92% or more.In addition, these are extracted The extraction yield of scandium can be inhibited 3% hereinafter, can effectively be detached uranium with scandium by solvent extraction processing in processing.

Then, the raffinate obtained in the solvent extraction processing that the initial liquid H of composition is carried out is shown in for above-mentioned table 8 In (embodiment 2-4), the precipitation (scandium hydroxide) containing scandium is generated as neutralizer addition sodium hydroxide.Then, in the precipitation Hydrochloric acid solution is added in object, is completely dissolved, and the lysate (lysate of scandium) formed shown in the following table 10 has been obtained.

Table 10

* unit is [g/L], is [mg/L] to Th and U.

Then, for the scandium lysate by dissolving with hydrochloric acid shown in table 10, addition is calculated as molten relative to this with calculation amount 2 hydrate of oxalic acid (Mitsubishi Gas Co., Ltd. (ガ ス plants of formula meeting of Mitsubishi of the amount of 1.5 equivalents of the scandium amount for including in solution liquid Society) system) it crystal and makes it dissolve, it stirs at ambient temperature and carries out within 60 minutes mixing them is made to react, thus generate oxalic acid scandium White crystal precipitates.

Obtained oxalic acid scandium sediment is taken out by separation of solid and liquid, analyzes the content of the thorium and uranium in sediment. Its assay value is shown in the following table 11.

Table 11

As shown in table 11, the content of thorium is 70ppm, the content of uranium is 10ppm, can generate thorium, the content of uranium is reduced To the oxalic acid scandium sediment of very micro amount, thorium and uranium can effectively be made to be detached with as the scandium of sediment.

《Comparative example 1》

As comparative example 1, the initial liquid of extraction that will be formed shown in A~D of above-mentioned table 7 in the same manner as in Example 1 For solvent extraction.Specifically, under the same conditions as example 1 by these initial liquid of extraction and as Neutral-neutral Extractants TBP mixing, implementation extraction processing was stirred after 15 minutes by blender at normal temperatures.Thereafter, quiet after stirring It sets, with organic solvent and raffinate after separatory funnel separating and extracting, is analyzed respectively using ICP.

Forming for the raffinate handled by solvent extraction is indicated in the following table 12.In addition, in table 12 by the extraction when Chloride concentration indicated together as the concentration (moL/L) in raffinate.In addition, by being calculated in a manner of similarly to Example 1 The extraction yield shown in table 13 and Fig. 2 gone out.In addition, as described above, Fig. 2 is the extraction relative to chloride concentration for indicating each element Take the drafting figure of the relationship of rate.

Table 12

* unit is [g/L], is [mg/L] to Th and U.

* oxidation-reduction potential (ORP) [mV] is using Ag-AgCl electrodes as reference electrode.

Table 13

As shown in table 12 and table 13 and Fig. 2, when T-Cl concentration is less than 2.0moL/L, uranium extraction rate is 30% hereinafter, becoming It is low.If in addition, a concentration of 2.0moL/L of T-Cl, uranium extraction rate becomes 60% or more, further when T-Cl concentration is more than When 2.5moL/L, uranium can be extracted with 92% or more ratio, can effectively be detached with scandium.

About the thorium in acidity of hydrochloric acid solution, significantly detached as uranium although cannot be handled by solvent extraction, It is by carrying out the oxalic acid salinization processing for raffinate together, scandium can be made to precipitate and effectively be detached with thorium.

《Comparative example 2》

As comparative example 2, using with initial liquid H same compositions that composition is shown in the used above-mentioned table of embodiment 27 Acidity of hydrochloric acid solution does not implement solvent extraction processing to the acidity of hydrochloric acid solution, directly adds oxalic acid and carries out oxalic acid salinization processing. Oxalic acid salinization treatment conditions are same as Example 1.

The assay value of the oxalic acid scandium handled by the oxalic acid salinization is shown in the following table 14.It should be noted that In table 14, show together the assay value for the oxalic acid scandium handled by the oxalic acid salinization in embodiment 2 that table 11 was shown with And oxalates is carried out to the raffinate after the solvent extraction in comparative example 1 (comparative example 1-3) under the same conditions as in practical example 2 Change the assay value of treated oxalic acid scandium.

Table 14

As shown in table 14, in comparative example 2, solvent extraction processing is not carried out, it is molten to the acidity of hydrochloric acid containing scandium, uranium, thorium In the case that liquid directly implements oxalic acid salinization processing, the result is that the uranium grade in obtained oxalic acid scandium is 60ppm, with embodiment 1 Compared to containing more uranium.It should be noted that even if the raffinate after the solvent extraction to being obtained by comparative example 1 implements grass In the case of hydrochlorateization processing, uranium grade is also 50ppm.

[comparative example 3]

As comparative example 3, using with initial liquid H same compositions that composition is shown in used above-mentioned table 7 in embodiment 2 Acidity of hydrochloric acid solution does not implement solvent extraction processing to the acidity of hydrochloric acid solution, directly adds sodium hydroxide generation and contains scandium Hydroxide (scandium hydroxide) precipitates.Thereafter, it is handled without oxalic acid salinization, directly analyzes obtained scandium hydroxide.It will The assay value of the scandium hydroxide is shown in the following table 15.

Table 15

As shown in Table 15, in comparative example 3, the thorium grade in scandium hydroxide is 1000ppm.With obtained by embodiment 2 The assay value of oxalic acid scandium after oxalic acid salinization compares it is found that all not carried out because of solvent extraction processing, oxalic acid salinization processing, institute It is got higher with thorium grade and uranium grade, fails effectively to detach with scandium, fail effectively to purify scandium.

[comparative example 4]

As comparative example 4, the salt for the initial liquid H same compositions that composition is shown with used above-mentioned table 7 in embodiment 2 is used Sour acid solution adds hydroxide after the solvent extraction processing under the conditions of implementation is same as Example 2 in obtained raffinate Sodium generates hydroxide (scandium hydroxide) precipitation containing scandium.Thereafter, it handles, directly analyzes obtained without oxalic acid salinization Scandium hydroxide.The assay value of the scandium hydroxide is shown in the following table 16.

Table 16

As shown in table 16, in comparative example 4, the thorium grade in scandium hydroxide is 950ppm.About uranium, although passing through solvent Extraction processing can make it drop to the grade of 30ppm, if but only carry out solvent extraction processing, effectively thorium cannot be made to drop It is low, it may thus be appreciated that oxalic acid salinization processing is necessary processing to Separation of Thorium.

As can be observed from the foregoing, by the acid solution containing scandium, uranium, thorium using the solvent of Neutral-neutral Extractants extract It takes, further, later, oxalic acid salinization processing is implemented to obtained raffinate, thus, it is possible to which effectively scandium is detached with uranium and thorium, Obtain uranium grade and the low scandium of thorium grade.

Claims (8)

1. a kind of recovery method of scandium, wherein it has：

Process is leached, which is soaked by sulfuric acid leaches the nickel oxide ore containing scandium at high temperature under high pressure Go out liquid and leaches residue；

Neutralization step, the process neutralizer is added in the leachate and obtain neutralization precipitation object and in and rear liquid；

Vulcanization process, the process obtain nickel sulfide and liquid after vulcanization in described with vulcanizing agent is added in rear liquid；

Ion-exchange process, the process pass through the scandium in liquid after making liquid after the vulcanization contact with chelating resin to make the vulcanization It is adsorbed in the chelating resin, obtains scandium eluent；

Dissolution process, after which adds alkali in the scandium eluent and obtain scandium hydroxide sediment, in the hydroxide Acid solution is added in scandium and carries out sour dissolving, thus obtains the acid dissoluting liquid of scandium；

Solvent extraction step, the process make the acid dissoluting liquid contact Neutral-neutral Extractants of the scandium carry out the impurity other than extraction and separation scandium Element obtains the raffinate containing scandium；With

Scandium recovery process, the process add oxalic acid to generate the salt of oxalic acid scandium in the raffinate, roast the oxalic acid scandium salts and Obtain scandium oxide.

2. the recovery method of scandium according to claim 1, wherein

The chelating resin be using imino-diacetic acetic acid as the resin of functional group,

The ion-exchange process includes：

Absorption process, liquid contacts with the chelating resin and the scandium is made to be adsorbed in the chelating tree after which makes the vulcanization Fat；

Aluminium removing step, the process make 0.1N sulfuric acid solutions below and have adsorbed the chelating resin of scandium in the absorption process Contact, to which removal is adsorbed in the aluminium of the chelating resin in the absorption process；

Scandium elution procedure, the process make sulfuric acid solutions of the 0.3N less than 3N and the chelating after the experience aluminium removing step Resin contact obtains the scandium eluent；With

Chromium removing step, the process make the sulfuric acid solution of 3N or more with undergo that the chelating resin after the scandium elution procedure contacts and Removal is adsorbed in the chromium of the chelating resin in the absorption process.

3. the recovery method of scandium according to claim 1 or 2, wherein

In the solvent extraction step, the pH of the acid dissoluting liquid of the scandium is maintained into 1.0 or more and 2.5 ranges below, The acid dissoluting liquid of the scandium is set to be contacted with the Neutral-neutral Extractants.

4. the recovery method of scandium according to any one of claim 1 to 3, wherein

The solvent extraction step includes：

The acid dissoluting liquid of the scandium and organic solvent containing the Neutral-neutral Extractants are mixed, are separated by extraction process, the process Organic solvent and raffinate after the extraction of the impurity element other than scandium are extracted；

Cleaning process, the process by 1.0moL/L or more and the acid solution of 5.0moL/L or less concentration with it is organic molten after the extraction Agent mixes, the organic solvent after being washed from organic solvent recycling scandium after the extraction；With

It is stripped process, which adds strippant after the washing in organic solvent, from organic solvent after the washing It is stripped out impurity element and obtains anti-stripping agent.

5. the recovery method of scandium according to any one of claim 1 to 4, wherein

In the dissolution process, sour dissolving is carried out by adding salpeter solution in the scandium hydroxide, to obtain conduct The nitric acid lysate of the scandium of the acid dissoluting liquid of scandium.

6. the recovery method of scandium according to any one of claim 1 to 4, wherein

In the dissolution process, sour dissolving is carried out by adding hydrochloric acid solution in the scandium hydroxide, to obtain conduct The dissolving with hydrochloric acid liquid of the scandium of the acid dissoluting liquid of scandium.

7. the recovery method of scandium according to claim 6, wherein

It is in the solvent extraction step, the chloride of the dissolving with hydrochloric acid liquid of the scandium obtained in the dissolution process is dense Degree is adjusted to 2.0moL/L or more and 6.0moL/L hereinafter, the dissolving with hydrochloric acid liquid of the scandium is made to be contacted with the Neutral-neutral Extractants.

8. the recovery method of scandium according to any one of claim 1 to 7, wherein

The scandium recovery process includes：

The sodium hydroxide of 5.0moL/L or more and 8.0moL/L or less concentration are added to and obtained in the solvent extraction step The raffinate in, the process that obtains scandium hydroxide sediment；

Obtained scandium hydroxide sediment is used into sulfuric acid or dissolving with hydrochloric acid, grass is added in the lysate obtained from being dissolved Acid and the process that obtains oxalic acid scandium crystal；With

The process that the oxalic acid scandium crystal is burnt into.